EP2841407A1 - Unsaturated fatty alcohol compositions and derivatives from natural oil metathesis - Google Patents

Unsaturated fatty alcohol compositions and derivatives from natural oil metathesis

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Publication number
EP2841407A1
EP2841407A1 EP13720672.8A EP13720672A EP2841407A1 EP 2841407 A1 EP2841407 A1 EP 2841407A1 EP 13720672 A EP13720672 A EP 13720672A EP 2841407 A1 EP2841407 A1 EP 2841407A1
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Prior art keywords
oil
metathesis
unsaturated
derived
hydrocarbyl
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EP13720672.8A
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German (de)
English (en)
French (fr)
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Stephen A. Di Biase
Keith M. WAMPLER
David R. Allen
Randal J. Bernhardt
Ryan LITTICH
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Elevance Renewable Sciences Inc
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Elevance Renewable Sciences Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/007—Esters of unsaturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds

Definitions

  • Fatty alcohol derivatives are used across a broad array of industries and end uses, including personal care, laundry and cleaning, emulsion
  • Fatty alcohols are usually made by reducing the corresponding fatty acids or esters, typically by catalytic hydrogenation. Often, the catalyst includes zinc or copper and chromium.
  • U.S. Pat. No. 5,672,781 uses a CuCrO 4 catalyst to hydrogenate methyl esters from palm kernel oil, which has substantial unsaturation, to produce a mixture of fatty alcohols comprising about 52 wt.% of oleyl alcohol, a monounsaturated fatty alcohol.
  • the fatty acids or esters used to make fatty alcohols and their derivatives are usually made by hydrolysis or transesterification of triglycerides, which are typically animal or vegetable fats. Consequently, the fatty portion of the acid or ester will typically have 6-22 carbons with a mixture of saturated and internally unsaturated chains. Depending on source, the fatty acid or ester often has a preponderance of C 16 to C 22 component.
  • methanolysis of soybean oil provides the saturated methyl esters of palmitic (C 16 ) and stearic (C 18 ) acids and the unsaturated methyl esters of oleic (C 18 mono-unsaturated), linoleic (C 18 di- unsaturated), and ⁇ -linolenic (C 18 tri-unsaturated) acids.
  • the unsaturation in these acids has either exclusively or predominantly cis- configuration.
  • Soybean oil and palm oil can be more economical than, for example, coconut oil, which is a traditional starting material for making detergents.
  • metathesis relies on conversion of olefins into new products by rupture and reformation of carbon-carbon double bonds mediated by transition metal carbene complexes.
  • Self-metathesis of an unsaturated fatty ester can provide an equilibrium mixture of starting material, an internally unsaturated hydrocarbon, and an unsaturated diester. For instance, methyl oleate (methyl cis-9-octadecenoate) is partially converted to 9-octadecene and dimethyl 9-octadecene-1 ,18-dioate, with both products consisting predominantly of the trans- isomer.
  • Metathesis effectively isomerizes the cis- double bond of methyl oleate to give an equilibrium mixture of cis- and trans- isomers in both the“unconverted” starting material and the metathesis products, with the trans- isomers predominating.
  • Cross-metathesis of unsaturated fatty esters with olefins generates new olefins and new unsaturated esters that can have reduced chain length and that may be difficult to make otherwise.
  • cross-metathesis of methyl oleate and 3-hexene provides 3-dodecene and methyl 9-dodecenoate (see also U.S. Pat. No. 4,545,941).
  • Terminal olefins are particularly desirable synthetic targets, and Elevance Renewable Sciences, Inc. recently described an improved way to prepare them by cross-metathesis of an internal olefin and an ⁇ -olefin in the presence of a ruthenium alkylidene catalyst (see U.S. Pat.
  • the unsaturated alcohol compositions are obtained by reducing a metathesis-derived hydrocarbyl unsaturated ester.
  • a process for preparing an unsaturated alcohol composition is disclosed where a metathesis derived hydrocarbyl carbonyl compound is reacted in the presence of a silane compound, an organic solvent, and a catalyst system prepared from a metallic complex and a reducing agent. This mixture is then hydrolyzed with a metallic base, and then mixed with organic solvent. The resultant mixture is then separated, washed, dried, and/or purified, as individual steps or in combinations thereof, to produce the unsaturated alcohol composition.
  • Derivatives can be made by the polymerization of the metathesis-derived unsaturated alcohol with an individual or mixed alpha olefin stream.
  • a sulfurized derivative can be made by reacting the metathesis-derived unsaturated alcohol with a sulfurizing reagent.
  • An ester derivative can be made by reacting the metathesis-derived unsaturated alcohol with a carboxylic acid.
  • An amine derivative can be made by reacting the metathesis- derived unsaturated alcohol with an amine compound.
  • references to“a,”“an,” and/or“the” may include one or more than one, and that reference to an item in the singular may also include the item in the plural.
  • the invention relates to derivatives made by one or more of unsaturated fatty alcohol compositions.
  • the invention relates to fatty alcohol compositions which are made by reducing a metathesis-derived hydrocarbyl unsaturated ester.
  • a process for preparing an unsaturated alcohol composition is disclosed where a metathesis derived hydrocarbyl carbonyl compound is reacted in the presence of a silane compound, an organic solvent, and a catalyst system prepared from a metallic complex and a reducing agent. This mixture is then hydrolyzed with a metallic base, and then mixed with organic solvent. The resultant mixture is then separated, washed, dried, and/or purified, as individual steps or in combinations thereof, to produce the unsaturated alcohol composition.
  • the hydrocarbyl unsaturated ester preferably a C 5 -C 35 unsaturated alkyl ester, and more preferably a C 10 -C 17 unsaturated alkyl ester, used as a reactant is derived from metathesis of a natural oil.
  • the hydrocarbyl unsaturated esters are unsaturated alkyl esters.
  • these materials particularly the short-chain alkyl esters (e.g., methyl 9-decenoate or methyl 9-dodecenoate), have been difficult to obtain except in lab-scale quantities at considerable expense.
  • esters are now available in bulk at reasonable cost.
  • the hydrocarbyl unsaturated esters are conveniently generated by self-metathesis of natural oils or cross- metathesis of natural oils with olefins, preferably ⁇ -olefins, and particularly ethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like.
  • hydrocarbyl or“hydrocarbyl group,” when referring to groups attached to the remainder of a molecule, refers to one or more groups having a purely hydrocarbon or predominantly hydrocarbon character. These groups may include: (1) purely hydrocarbon groups (i.e., aliphatic (alkyl), alicyclic, aromatic, branched, aliphatic- and alicyclic-substituted aromatic,
  • any two indicated substituents may together form an alicyclic group
  • substituted hydrocarbon groups i.e, groups containing non-hydrocarbon substituents such as hydroxy, amino, nitro, cyano, alkoxy, acyl, halo, etc.
  • hetero groups i.e., groups which contain atoms, such as N, O or S, in a chain or ring otherwise composed of carbon atoms.
  • no more than about three substituents or hetero atoms, or no more than one, may be present for each 10 carbon atoms in the hydrocarbyl group.
  • the hydrocarbyl group may contain one, two, three, or four carbon-carbon double bonds.
  • Non-limiting examples of procedures for making hydrocarbyl unsaturated esters by metathesis are disclosed in WO 2008/048522, the contents of which are incorporated herein by reference.
  • Examples 8 and 9 of WO 2008/048522 may be employed to produce methyl 9-decenoate and methyl 9- dodecenoate. Suitable procedures also appear in U.S. Pat. Appl. Publ. No.
  • At least a portion of the hydrocarbyl unsaturated ester has “ ⁇ 9 ” unsaturation, i.e., the carbon-carbon double bond in the ester is at the 9- position with respect to the ester carbonyl.
  • an alkyl chain of 1 to 7 carbons, respectively is attached to C10.
  • the unsaturation is at least 1 mole % trans- ⁇ 9 , more preferably at least 25 mole % trans- ⁇ 9 , more preferably at least 50 mole % trans- ⁇ 9 , and even more preferably at least 80% trans- ⁇ 9 .
  • the unsaturation may be greater than 90 mole %, greater than 95 mole %, or even 100% trans- ⁇ 9 .
  • naturally sourced fatty esters that have ⁇ 9 unsaturation e.g., methyl oleate, usually have ⁇ 100% cis- isomers.
  • trans- geometry (particularly trans- ⁇ 9 geometry) may be desirable in the metathesis-derived unsaturated fatty alcohol derivatives of the invention
  • the skilled person will recognize that the configuration and the exact location of the carbon-carbon double bond will depend on reaction conditions, catalyst selection, and other factors. Metathesis reactions are commonly accompanied by isomerization, which may or may not be desirable. See, for example, G. Djigoué and M. Meier, Appl. Catal., A 346 (2009) 158, especially Fig. 3.
  • the skilled person might modify the reaction conditions to control the degree of isomerization or alter the proportion of cis- and trans- isomers generated. For instance, heating a metathesis product in the presence of an inactivated metathesis catalyst might allow the skilled person to induce double bond migration to give a lower proportion of product having trans- ⁇ 9 geometry.
  • An elevated proportion of trans- isomer content (relative to the usual all-cis configuration of the naturally derived hydrocarbyl unsaturated ester) imparts different physical properties to unsaturated fatty alcohol derivatives, including, for example, modified physical form, melting range, compactability, and other important properties. These differences should allow formulators that use unsaturated fatty alcohol derivatives greater latitude or expanded choice as they use them in cleaners, detergents, personal care, agricultural uses, specialty foams, and other end uses.
  • Suitable metathesis-derived hydrocarbyl unsaturated esters derive from carboxylic acids.
  • the esters derive from C 5 -C 35 carboxylic acids, more preferably from C 10 -C 17 carboxylic acids.
  • Examples include esters derived from 9-decylenic acid (9-decenoic acid), 9-undecenoic acid, 9-dodecylenic acid (9- dodecenoic acid), 9-tridecenoic acid, 9-tetradecenoic acid, 9-pentadecenoic acid, 9- hexadecenoic acid, 9-heptadecenoic acid, and the like.
  • cross-metathesis or self-metathesis of the natural oil is followed by separation of an olefin stream from a modified oil stream, typically by stripping or distilling out the more volatile olefins.
  • the modified oil stream is then reacted with a lower alcohol, typically methanol, to give glycerin and a mixture of alkyl esters.
  • This mixture normally includes saturated C 6 -C 22 alkyl esters, predominantly C 16 -C 18 alkyl esters, which are essentially spectators in the metathesis reaction. The rest of the product mixture depends on whether cross- or self- metathesis is used.
  • the resulting hydrocarbyl unsaturated ester mixture includes a C 10 unsaturated alkyl ester and one or more C 11 to C 17 unsaturated alkyl ester coproducts in addition to the glycerin by-product.
  • the terminally unsaturated C 10 product is accompanied by different coproducts depending upon which ⁇ -olefin(s) is used as the cross-metathesis reactant.
  • 1 - butene gives a C 12 unsaturated alkyl ester
  • 1-hexene gives a C 14 unsaturated alkyl ester
  • the unsaturated alkyl esters are readily separated from each other and easily purified by fractional distillation.
  • Natural oils suitable for use as a feedstock to generate the hydrocarbyl unsaturated esters from self-metathesis or cross-metathesis with olefins are well known. Suitable natural oils include vegetable oils, algal oils, animal fats, tall oils, derivatives of the oils, and combinations thereof.
  • suitable natural oils include, for example, soybean oil, palm oil, rapeseed oil, coconut oil, palm kernel oil, sunflower oil, safflower oil, sesame oil, corn oil, olive oil, peanut oil, cottonseed oil, canola oil, castor oil, linseed oil, tung oil, jatropha oil, mustard oil, pennycress oil, camellina oil, coriander oil, almond oil, wheat germ oil, bone oil, tallow, lard, poultry fat, fish oil, and the like. Soybean oil, palm oil, rapeseed oil, and mixtures thereof are preferred natural oils.
  • Genetically modified oils e.g., high-oleate soybean oil or genetically modified algal oil
  • Preferred natural oils have substantial unsaturation, as this provides a reaction site for the metathesis process for generating olefins.
  • Particularly preferred are natural oils that have a high content of unsaturated fatty groups derived from oleic acid.
  • particularly preferred natural oils include soybean oil, palm oil, algal oil, canola oil, and rapeseed oil.
  • a modified natural oil such as a partially hydrogenated vegetable oil or an oil modified by a fermentation process, can be used instead of or in combination with the natural oil.
  • a natural oil is partially hydrogenated or modified by fermentation
  • the site of unsaturation can migrate to a variety of positions on the hydrocarbon backbone of the fatty ester moiety.
  • the reaction products will have a different and generally broader distribution compared with the product mixture generated from an unmodified natural oil.
  • the products generated from the modified natural oil are similarly converted to inventive unsaturated alcohol derivative compositions.
  • the naturally occurring oil may be refined, bleached, and/or deodorized.
  • the other reactant in the cross-metathesis reaction is an olefin.
  • Suitable olefins are internal or ⁇ -olefins having one or more carbon-carbon double bonds, and having between about 2 to about 30 carbon atoms. Mixtures of olefins can be used.
  • the olefin is a monounsaturated C 2 -C 10 ⁇ -olefin, more preferably a monounsaturated C 2 -C 8 ⁇ -olefin.
  • Preferred olefins also include C 4 -C 9 internal olefins.
  • suitable olefins for use include, for example, ethylene, propylene, 1 -butene, cis- and trans-2-butene, 1-pentene, isohexylene, 1-hexene, 3- hexene, 1-heptene, 1-octene, 1 -nonene, 1-decene, and the like, and mixtures thereof.
  • Cross-metathesis is accomplished by reacting the natural oil and the olefin in the presence of a homogeneous or heterogeneous metathesis catalyst.
  • the olefin is omitted when the natural oil is self-metathesized, but the same catalyst types are generally used.
  • Suitable homogeneous metathesis catalysts include combinations of a transition metal halide or oxo-halide (e.g., WOCl 4 or WCl 6 ) with an alkylating cocatalyst (e.g., Me 4 Sn).
  • Preferred homogeneous catalysts are well- defined alkylidene (or carbene) complexes of transition metals, particularly Ru, Mo, or W. These include first and second-generation Grubbs catalysts, Grubbs-Hoveyda catalysts, and the like.
  • Suitable alkylidene catalysts have the general structure:
  • M is a Group 8 transition metal
  • L 1 , L 2 , and L 3 are neutral electron donor ligands
  • n is 0 (such that L 3 may not be present) or 1
  • m is 0, 1, or 2
  • X 1 and X 2 are anionic ligands
  • R 1 and R 2 are independently selected from H, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom- containing hydrocarbyl, and functional groups. Any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 and R 2 can form a cyclic group and any one of those groups can be attached to a support.
  • Second-generation Grubbs catalysts also have the general formula described above, but L 1 is a carbene ligand where the carbene carbon is flanked by N, O, S, or P atoms, preferably by two N atoms. Usually, the carbene ligand is part of a cyclic group. Examples of suitable second-generation Grubbs catalysts also appear in the‘086 publication. [0027] In another class of suitable alkylidene catalysts, L 1 is a strongly coordinating neutral electron donor as in first- and second-generation Grubbs catalysts, and L 2 and L 3 are weakly coordinating neutral electron donor ligands in the form of optionally substituted heterocyclic groups. Thus, L 2 and L 3 are pyridine, pyrimidine, pyrrole, quinoline, thiophene, or the like.
  • a pair of substituents is used to form a bi- or tridentate ligand, such as a biphosphine, dialkoxide, or alkyldiketonate.
  • Grubbs-Hoveyda catalysts are a subset of this type of catalyst in which L 2 and R 2 are linked .
  • a neutral oxygen or nitrogen coordinates to the metal while also being bonded to a carbon that is ⁇ -, ⁇ -, or ⁇ - with respect to the carbene carbon to provide the bidentate ligand. Examples of suitable Grubbs-Hoveyda catalysts appear in the‘086 publication.
  • Heterogeneous catalysts suitable for use in the self- or cross- metathesis reaction include certain rhenium and molybdenum compounds as described, e.g., by J.C. Mol in Green Chem. 4 (2002) 5 at pp. 11-12. Particular examples are catalyst systems that include Re 2 O 7 on alumina promoted by an alkylating cocatalyst such as a tetraalkyl tin lead, germanium, or silicon compound. Others include MoCl 3 or MoCl 5 on silica activated by tetraalkyltins. [0031] For additional examples of suitable catalysts for self- or cross- metathesis, see U.S. Pat. No.
  • the unsaturated fatty alcohols are made by reacting a metathesis-derived hydrocarbyl unsaturated ester, preferably a C 5 -C 35 unsaturated alkyl ester, and more preferably a C 10 -C 17 unsaturated alkyl ester, with a reducing agent.
  • “unsaturated alcohols” typically have a hydrocarbyl chain length of between 6 and 24 carbon atoms.
  • the fatty alcohol may be an unsaturated alcohol such as 9-decen-1-ol or 9-dodecen- 1-ol.
  • the reducing agent is typically either a hydride reducing agent (sodium borohydride, lithium aluminum hydride, or the like) or molecular hydrogen in combination with a metal catalyst, frequently copper and/or zinc in combination with chromium, or a silane compound in combination with a metallic complex catalyst (see, e.g., U.S. Pat. Nos.
  • ester hydrogenation catalysts are not always completely selective, a minor proportion of the carbon-carbon double bonds, typically 10% or less, might be hydrogenated during the ester reduction, resulting in a mixed product that may have up to 10% of saturated fatty alcohols in addition to the desired unsaturated fatty alcohols.
  • the process to prepare the unsaturated alcohols of the present invention is characterized in that a carbonyl compound, in particular, a hydrocarbyl unsaturated ester, is reacted with stoichiometric amounts of a silane compound, in the presence of a catalyst system prepared from a metallic complex and a reducing agent.
  • the unsaturated alcohols comprise 9-decen-1 -ol or 9-dodecen-1 -ol
  • the hydrocarbyl unsaturated ester comprises methyl-9- decenoate or methyl-9-dodecenoate.
  • the silane compound can be selected from the group consisting of alkyltrihydrosilanes, aryltrihydrosilanes, dialkyldihydrosilanes, diaryldihydrosilanes, trialkylhydrosilanes, triarylhydrosilanes, alkylhydrosiloxanes, arylhydrosiloxanes, polyalkylhydrosiloxanes and the like, individually or in combinations thereof.
  • the silane compound is polymethylhydrosiloxane.
  • the catalyst system can be obtained in situ, in the reaction medium or be prepared separately, and comprises a metallic complex of general formula MX n , wherein M represents a transition metal selected from the group consisting of zinc, cadmium, manganese, cobalt, iron, copper, nickel, ruthenium and palladium, X an anion comprising a halide, a carboxylate or any anionic ligand, wherein X is selected from the group consisting of chloride, bromide, iodide, carbonate, isocyanate, cyanide, phosphate, acetate, propionate, 2-ethylhexanoate, stearate or naphthenate of one of the above-mentioned metals, individually or in combinations thereof, and n is a number comprised between 1 and 4.
  • M represents a transition metal selected from the group consisting of zinc, cadmium, manganese, cobalt, iron, copper, nickel, ruthenium and palladium
  • X
  • M is zinc
  • X is a carboxylate such as 2-ethylhexanoate
  • n is 2
  • the reducing agent is sodium borohydride, thus providing for a zinc 2-ethylhexanoate complex.
  • the metallic complex and reducing agent may be mixed with an inert organic solvent, for example, an ether such as methyltertbutylether, diisopropylether, dioxane, tetrahydrofuran, ethyleneglycol dimethylether, or an aliphatic hydrocarbon such as heptane, petroleum ether, octane, cyclohexane, or aromatic as benzene, toluene, xylene or mesitylene, individually or in combinations thereof.
  • an ether such as methyltertbutylether, diisopropylether, dioxane, tetrahydrofuran, ethyleneglycol dimethylether, or an aliphatic hydrocarbon such as heptane, petroleum ether, octane, cyclohexane, or aromatic as benzene, toluene, xylene or mesitylene, individually or in combinations thereof.
  • the solvent is diisoprop
  • the chosen metallic complex preferably zinc 2-ethylhexanoate
  • the reducing agent preferably sodium borohydride
  • an appropriate organic solvent preferably diisopropyl ether
  • the carbonyl compound preferably an unsaturated hydrocarbyl ester such as methyl-9-decenoate or methyl-9-dodecenoate
  • the resulting solution is hydrolyzed by reacting the solution with an aqueous or alcoholic solution of a metallic base, such as sodium hydroxide, potassium hydroxide, calcium oxide or sodium carbonate (preferably potassium hydroxide), individually or in combinations thereof, and then adding an appropriate organic solvent. Once the hydrolysis is complete, formation of two phases is generally observed, with the desired alcohol being in the organic phase. This organic phase is then separated, washed, dried, and /or purified, as individual steps or in combination thereof, to produce the unsaturated alcohol.
  • a metallic base such as sodium hydroxide, potassium hydroxide, calcium oxide or sodium carbonate (preferably potassium hydroxide)
  • the unsaturated alcohol can be produced by the selective hydrogenation of methyl oleate (methyl-9-octadecenoate) into oleyl alcohol (methyl-9-octadecen-1-ol). This hydrogenation can be carried out over bimetallic catalysts containing cobalt and tin, or ruthenium and tin. Other methods to produce unsaturated alcohols are provided in U.S. Patent Nos. 5364986 and 6229056, the teachings of which are incorporated herein by reference.
  • Suitable hydrocarbyl unsaturated esters can be generated by transesterifying a metathesis-derived triglyceride. For example, cross-metathesis of a natural oil with an olefin, followed by removal of unsaturated hydrocarbon metathesis products by stripping, and then transesterification of the modified oil component with a lower alkanol under basic conditions provides a mixture of hydrocarbyl unsaturated esters, preferably unsaturated alkyl esters.
  • hydrocarbyl unsaturated ester mixture can be purified to isolate particular alkyl esters prior to making the unsaturated alcohols and inventive derivatives.
  • “derivatives” includes not only chemical compositions or materials resulting from the reaction of unsaturated fatty alcohol(s) with at least one other reactant to form a reaction product, and further downstream reaction products of those reaction products as well, but does not include chemical compositions or materials that result from the reaction of unsaturated fatty alcohols with at least one alkoxylating, sulfating, sulfonating, or sulfitating agent.
  • the unsaturated alcohol may be further reacted into one or more alcohol derivatives, wherein such alcohol derivatives may be generated by dehydration of an alcohol to form alkenes, oxidation of an alcohol to form aldehydes or ketones, substitution of an alcohol to form alkyl halides, and esterification.
  • alcohol derivatives can have a very large variety of structures and include linear-, branched- or cyclic-aliphatic monoalcohol derivatives, diol derivatives and/or polyol derivatives; and aromatic or heterocyclic alcohol derivatives including natural alcohol derivatives, e.g., sugars and/or heteroatom-functional aliphatic alcohol derivatives such as aminoalcohol derivatives.
  • alcohol derivatives can be saturated or unsaturated, linear or have branches of a great variety of types known in the art depending on the size and position of branching moieties or, in other terms, analytical characterization (e.g., by NMR), performance properties, or the process by which the alcohol derivatives are made.
  • saccharide-derived fatty alcohol compositions readily derived from the disclosed unsaturated alcohols include alkyl polyglucosides. These all-natural alkyl polyglucosides can serve as nonionic surfactants, and are prepared by acid-catalyzed direct glycosidation of unsaturated fatty alcohols, or
  • Anionic derivatives may also be prepared from alkyl polyglucosides by sulfation (e.g., with chlorosulfonic acid, oleum, sulfur trioxide, etc.), phosphorylation (e.g., with dibenzyl diisopropylamino phosphoramidite), esterification (e.g., with maleic anhydride, citric acid) and subsequent sulfation/phosphorylation, and glucose C 6 -alcohol selective oxidation to the corresponding carboxylate.
  • sulfation e.g., with chlorosulfonic acid, oleum, sulfur trioxide, etc.
  • phosphorylation e.g., with dibenzyl diisopropylamino phosphoramidite
  • esterification e.g., with maleic anhydride, citric acid
  • glucose C 6 -alcohol selective oxidation to the corresponding carboxylate e.g., glucose C 6 -alcohol
  • alkyl glyceryl ethers Other accessible saccharide-based unsaturated fatty alcohol compositions are alkyl glyceryl ethers.
  • Alkyl glyceryl ethers are prepared by the alkylation of unsaturated fatty alcohols with glycidol, in the presence of an acidic or alkaline catalyst. The hydrophile-lipophile balance of this class of nonionic surfactant is readily modified by the number of glycidol moieties added to the fatty alcohol substrate.
  • Alkyl glyceryl ether derivatives may be further transformed into anionic surfactants by sulfation using any of the conventional reagents (chlorosulfonic acid, oleum, sulfur trioxide, etc.).
  • amphiphilic derivatives are accessible from the unsaturated alcohols disclosed herein.
  • a number of anionic surfactants may be prepared, including di-basic sulfosuccinate half esters and mono-basic sulfosuccinate diesters. These mono- and diesters are derived from maleic anhydride by ring-opening esterification with fatty alcohols then Michael addition of aqueous sodium bisulfite to the intermediate maleic acid mono- or diester.
  • Mono- and dibasic acid esters of phosphoric acid may be prepared by phosphorylation (“phosphation”) of fatty alcohols using phosphorus pentoxide. Owing to the presence of polyphosphoric acid and o-phosphoric acid in phosphorus pentoxide, molar ratios of mono- to diester of ⁇ 1.2:1 are generally observed.
  • Triesters of phosphoric acid conversely, are most readily prepared by esterification using phosphorus oxychloride in the presence of a tertiary amine as HCl scavenger.
  • oxyalkylenated unsaturated fatty alcohols may be used as substrates in the preparation of the above alkenyl sulfosuccinates, alkenyl phosphates, alkenyl glyceryl ethers.
  • certain derivatives such as polymerized materials can be generated by reacting an individual or mixed alpha olefins stream with unsaturated alcohols, preferably metathesis-derived unsaturated alcohols.
  • Such polymerized materials can be useful as synthetic base stocks for preparing lubricants or functional fluids, wherein such synthetic base stocks provide good solvency and lubricity while being miscible with conventional hydrocarbon lubricants. Such polymerized materials can also be useful as an additive that can be
  • 9-decen-1-ol derived from methyl-9-decenoate, with individual or mixed alpha olefins such as 1-decene and/or 1-dodecene can be polymerized to make synthetic base stocks for preparing lubricants or functional fluids, or as an additive in a finished lubricant.
  • the polymerization can be carried out using conventional polymerization techniques.
  • the polymerization may comprise a batch process, a continuous process, or a staged process. Polymerization may be effected either via the one or more carbon-carbon double bonds, the functional groups and/or the additional functionality provided by the reactants.
  • polymerization may involve employing one or more cationic, free radical, anionic, Ziegler-Natta, organometallic, metallocene, or ring-opening metathesis
  • Free radical initiators may include azo
  • the azo compounds may include azobisisobutyronitrile (AIBN), 1 , 1 '- azobis(cyclohexanecarbonitrile), and the like, and combinations thereof.
  • AIBN azobisisobutyronitrile
  • 1 , 1 '- azobis(cyclohexanecarbonitrile) azobisisobutyronitrile
  • the peroxide compounds may include benzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxide, di-tert-butylperoxide, t-butyl peroxy benzoate, di-t-amyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl perpivalate, di-tert-amyl peroxide, dicetyl peroxydicarbonate, tert -butyl peracetate, 2,2-bis(tert-butylperoxy)butane, 2,5- bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, 2,5-bis(tert-butylperoxy)-2,5- dimethylhexane, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, and the like, and combinations thereof.
  • the free radical initiator may comprise di
  • Suitable chain transfer agents may include dodecanethiol, t-nonylthiol, tetramethylsilane, cyclopropane, methane, t-butanol, ethane, ethylene oxide, 2,2-dimethylpropane, benzene, carbon tetrachloride, and bromotrichloromethane.
  • the acid catalyst may comprise a Lewis Acid, a Br ⁇ nsted acid, or a combination thereof.
  • the Lewis acids may include boron triflouride (BF 3 ), AlCl 3 , zeolite, and the like, and complexes thereof, and combinations thereof.
  • Br ⁇ nsted acids may include HF, HCl, phosphoric acid, acid clay, and the like, and combinations thereof.
  • Polymerization may be achieved using a promoter (e.g., an alcohol) or a dual promoter (e.g., an alcohol and an ester) as described U.S. Patents 7,592,497 B2 and 7,544,850 B2, the teachings of which are incorporated by reference.
  • a promoter e.g., an alcohol
  • a dual promoter e.g., an alcohol and an ester
  • the polymerization catalysts described herein may be supported on a support.
  • the catalysts may be deposited on, contacted with, vaporized with, bonded to, incorporated within, adsorbed or absorbed in, or on, one or more supports or carriers.
  • the catalysts described herein may be used individually or as mixtures.
  • the polymerizations using multiple catalysts may be conducted by addition of the catalysts simultaneously or in a sequence.
  • Lewis acid catalyst such as boron triflouride
  • 9-decen-1 -ol or 9-dodecen-1 -ol can serve as the alcohol promoter in the reaction, allowing for superior economics.
  • unsaturated alcohols can be reacted with sulfurizing reagents, such as solid, particulate, or molten forms of elemental sulfur, sulfur halides, hydrogen sulfide, phosphorus sulfide, aromatic sulfide, alkyl sulfide, sulfurized olefin, sulfurized oil, sulfurized fatty ester, diester sulfide, or a mixture of two or more thereof.
  • sulfurizing reagents such as solid, particulate, or molten forms of elemental sulfur, sulfur halides, hydrogen sulfide, phosphorus sulfide, aromatic sulfide, alkyl sulfide, sulfurized olefin, sulfurized oil, sulfurized fatty ester, diester sulfide, or a mixture of two or more thereof.
  • Such reaction can generate hydrocarbyl sulfur containing materials useful in specialty chemical applications including but not limited to lubricants or functional fluids, or as an additive in a finished lubric
  • reactions of the alcohol moiety in an unsaturated alcohol may create new monomers useful in making high performance polymers and oligomers.
  • Some non-limiting examples are reacting the alcohol moiety with carboxylic acids to make olefinic esters which can be polymerized using the methods mentioned above.
  • These carboxylic acids may comprise one or more monobasic and/or polybasic unsaturated carboxylic acids.
  • the monobasic carboxylic acids may comprise one or more compounds represented by the formula
  • R 1 and R 2 are independently hydrogen or hydrocarbyl groups.
  • R 1 and R 2 independently may be hydrocarbyl groups containing 5 to about 35 carbon atoms, or from 1 to about 12 carbon atoms, or from 1 to about 4 carbon atoms.
  • the polybasic carboxylic acid may comprise one or more alpha, beta, or internally unsaturated dicarboxylic acids. These may include those wherein a carbon-carbon double bond is in an alpha, beta, or internal position to at least one of the carboxy functions, or in an alpha, beta, internal position to both of the carboxy functions.
  • the carboxy functions of these compounds may be separated by up to about 4 carbon atoms, or about 2 carbon atoms.
  • the olefinic esters may comprise a hydrocarbyl chain of from about 3 to about 35 carbon atoms, or from about 6 to about 24 carbon atoms, or from about 8 to about 18 carbon atoms, or about 10 to 12 carbon atoms, and 1 , 2, 3 or 4 internal carbon-carbon double bonds.
  • the alcohol group can be further reacted with an amine to give an olefinic amine which may have unique properties when evaluated alone and in combination with adjuvants in the aforementioned applications.
  • the amine may contain one or more primary and/or secondary amino groups, or be a mono- substituted amine, di-substituted amine, poly-substituted amine, or a mixture of two or more thereof.
  • the olefinic amine can have high value as a novel monomer for making lubricants or functional fluids or as an additive in a finished lubricant.
  • Polymers made from the unsaturated alcohol and amine can be further reacted with electrophiles to yield derivatives useful as plasticizers, lubricants lubricant additives and intermediates, antimicrobial, friction reducing agents, plastics, coatings, adhesives and other compositions.
  • Primary and secondary amines arising from the amination of unsaturated fatty alcohols may be further derivatized on treatment with acrylonitrile, in the presence of a suitable alkaline or acidic catalyst.
  • the resulting mono- or di- cyanoethylated amines, products of Michael addition are often reduced to provide the corresponding propylamines (e.g. polyamines). This process of Michael addition, and then reduction, can be performed iteratively to produce higher polyamines.
  • Primary, secondary, and tertiary amines derived from unsaturated fatty alcohols may be derivatized via salt formation, employing a wide variety of mineral and organic acids (e.g., acetic acid) in the production of such fatty amine salts.
  • the resulting amine salts have utility in a variety of applications, for example, as dispersants and anti-caking agents in agrochemical, petrochemical and water remediation applications.
  • products made in accordance with the invention are typically mixtures of cis- and trans- isomers. Except as otherwise indicated, all of the structural representations provided herein show only a trans- isomer. The skilled person will understand that this convention is used for convenience only, and that a mixture of cis- and trans- isomers is understood unless the context dictates otherwise. Structures shown often refer to a principal product that may be accompanied by a lesser proportion of other components or positional isomers. Thus, the structures provided represent likely or predominant products. [0060] Some specific examples of C 10 , C 12 , C 14 , and C 16 -based unsaturated alcohols used to make inventive derivatives appear below:
  • the fatty alcohol compositions have the general structure:
  • R-CH CH-(CH 2 ) 7 -CH 2 OH
  • R is H or C 2 -C 7 alkyl.
  • the invention includes a process for making derivatives.
  • the process comprises first reducing a metathesis-derived hydrocarbyl unsaturated ester, preferably a C 5 -C 35 unsaturated alkyl ester, and more preferably a C 10 -C 17 unsaturated alkyl ester, to produce an unsaturated fatty alcohol composition.
  • the fatty alcohol composition is then converted to a derivative. Suitable reagents and processes for effecting the reduction have already been described.
  • a composition comprising at least one unsaturated fatty alcohol derivative is provided.
  • the composition may be an aqueous system or provided in other forms.
  • the unsaturated fatty alcohol derivatives described herein may be incorporated into various formulations and used as lubricants, functional fluids, fuels and fuel additives, additives for such lubricants, functional fluids and fuels, plasticizers, asphalt additives, friction reducing agents, antistatic agents in the textile and plastics industries, flotation agents, gelling agents, epoxy curing agents, corrosion inhibitors, pigment wetting agents, in cleaning compositions, plastics, coatings, adhesives, surfactants, emulsifiers, skin feel agents, film formers, rheological modifiers, solvents, release agents, conditioners, and dispersants, hydrotropes, etc.
  • such formulations may be used in end-use applications including, but not limited to, personal care, as well as household and industrial and institutional cleaning products, oil field applications, gypsum foamers, coatings, adhesives and sealants, agricultural formulations, to name but a few.
  • the unsaturated fatty alcohol derivatives described herein may be employed as or used in applications including, but not limited to bar soaps, bubble baths, shampoos, conditioners, body washes, facial cleansers, hand soaps/washes, shower gels, wipes, baby cleansing products, creams/lotions, hair treatment products, anti- perspirants/deodorants, enhanced oil recovery compositions, solvent products, gypsum products, gels, semi-solids, detergents, heavy duty liquid detergents (HDL), light duty liquid detergents (LDL), liquid detergent softener antistat formulations, dryer softeners, hard surface cleaners (HSC) for household, autodishes, rinse aids, laundry additives, carpet cleaners, softergents, single rinse fabric softeners, I&I laundry, oven cleaners, car washes, transportation cleaners, drain cleaners, defoamers, anti-foamers, foam boosters, anti-dust/dust repellants, industrial cleaners, institutional cleaners, janitorial
  • the unsaturated alcohol derivatives may be incorporated into, for example, various compositions and used as lubricants, functional fluids, fuels, additives for such lubricants, functional fluids and fuels, plasticizers, asphalt additives and emulsifiers, friction reducing agents, plastics, coatings, adhesives, surfactants, emulsifiers, skin feel agents, film formers, rheological modifiers, biocides, biocide potentiators, solvents, release agents, conditioners, and dispersants, etc.
  • compositions may be used in end-use applications including, but not limited to, personal care liquid cleansing products, conditioning bars, oral care products, household cleaning products, including liquid and powdered laundry detergents, liquid and sheet fabric softeners, hard and soft surface cleaners, sanitizers and disinfectants, and industrial cleaning products, emulsion polymerization, including processes for the manufacture of latex and for use as surfactants as wetting agents, dispersants, solvents, and in agriculture applications as formulation inerts in pesticide applications or as adjuvants used in conjunction with the delivery of pesticides including agricultural crop protection turf and ornamental, home and garden, and professional applications, and institutional cleaning products.
  • They may also be used in oil field applications, including oil and gas transport, production, stimulation and drilling chemicals and reservoir conformance and enhancement, organoclays for drilling muds, specialty foamers for foam control or dispersancy in the manufacturing process of gypsum, cement wall board, concrete additives and firefighting foams, paints and coatings and coalescing agents, paint thickeners, adhesives, or other applications requiring cold tolerance performance or winterization (e.g., applications requiring cold weather performance without the inclusion of additional volatile components).
  • oil field applications including oil and gas transport, production, stimulation and drilling chemicals and reservoir conformance and enhancement, organoclays for drilling muds, specialty foamers for foam control or dispersancy in the manufacturing process of gypsum, cement wall board, concrete additives and firefighting foams, paints and coatings and coalescing agents, paint thickeners, adhesives, or other applications requiring cold tolerance performance or winterization (e.g., applications requiring cold weather performance without the inclusion of additional volatile components).
  • the formulations mentioned above commonly contain, in addition to the unsaturated alcohol derivatives disclosed herein, one or more other components for various purposes, such as surfactants, anionic surfactants, cationic surfactants, ampholtyic surfactants, zwitterionic surfactants, mixtures of surfactants, builders and alkaline agents, enzymes, adjuvants, fatty acids, odor control agents and polymeric suds enhancers, and the like.
  • surfactants anionic surfactants, cationic surfactants, ampholtyic surfactants, zwitterionic surfactants, mixtures of surfactants, builders and alkaline agents, enzymes, adjuvants, fatty acids, odor control agents and polymeric suds enhancers, and the like.
  • the ester solution is added dropwise to the LAH suspension at a rate that maintains the reaction temperature below 20 o C.
  • the funnel is refilled with pure ester (750 g; total of 1000 g) due to the large volume of the reaction mixture, and the addition continues. Total addition time of the ester: 5 h. Once the addition is complete, the reaction temperature is ⁇ 15 o C and stirring continues for 30 min. 1 H NMR analysis shows complete conversion of the ester to the desired alcohol.
  • Deionized water (135 g) is added slowly via the addition funnel while keeping the temperature below 20°C. Hydrogen evolution appears to cease after approximately half of the water is added. The viscosity of the mixture increases, but it remains stirrable. The flask is removed from the cooling bath, and aqueous sodium hydroxide (15% aq. NaOH, 135 g) is added. During this addition, the reaction mixture thickens and quickly becomes an unstirrable slurry that has to be broken up with a spatula. Addition of the remaining NaOH solution proceeds without incident. Following the 15% NaOH addition, deionized water (3 X 135 g) is added. The slurry stirs for 20 min. and then stands overnight at room temperature.
  • A10-1 The procedure used to prepare A10-1 is generally followed using THF (3 L), lithium aluminum hydride pellets (116 g), and methyl 9-dodecenoate (1000 g total).
  • Methyl 9-decenoate (lot no. 184-133) and methyl 9- dodecenoate (lot no. 184-133) were obtained from Materia, Inc. (Pasadena, CA).
  • Poly(methylhydrosiloxane) Alfa-Aesar, Ward Hill, MA; lot no. 10111148
  • methyl 9-decenoate (10.00 g, 54.26 mmol) was added to the prepared catalyst solution and then the flask was fitted with a reflux condenser and placed in a silicone oil bath. The solution was then brought to reflux under air for three hours, after which time polymethylhydrosiloxane (PMHS) (7.765 g, 119.3 mmol) was added and the solution was refluxed for an additional three hours. The slightly turbid, colorless solution was then cooled to room temperature and slowly treated with a solution of 10 g KOH in 30 mL of water. The reaction proceeded first with hydrogen gas evolution, due to excess silane, and then the formation of a white precipitate.
  • PMHS polymethylhydrosiloxane

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Effective date: 20170717